TWI401233B - 多層陶瓷電容器內之介質陶瓷組成物及其電容器之形成方法 - Google Patents

多層陶瓷電容器內之介質陶瓷組成物及其電容器之形成方法 Download PDF

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TWI401233B
TWI401233B TW095141984A TW95141984A TWI401233B TW I401233 B TWI401233 B TW I401233B TW 095141984 A TW095141984 A TW 095141984A TW 95141984 A TW95141984 A TW 95141984A TW I401233 B TWI401233 B TW I401233B
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Taiwan
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component
group
capacitor
composition
oxide
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TW095141984A
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TW200722403A (en
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Michael S Randall
Abhijit Gurav
Pascal Pinceloup
Azizuddin Tajuddin
Ian Burn
Thomas S Poole
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Kemet Electronics Corp
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Description

多層陶瓷電容器內之介質陶瓷組成物及其電容器之形成方法
本案係關於陶瓷電容器，具有貴金屬或基礎金屬電極，對溫度係數標準C0G，符合電子工業聯盟(EIA)標準第198－1－F－2002號。更具體而言，本案係關於陶瓷電容器，具有陶瓷介質組成物，均質塗佈以摻雜劑、助熔劑和/或其他改質劑，以製成高度均質之化學物，用於下一代薄層C0G裝置。
陶瓷介質配方常用來製造各種微電子裝置，包含陶瓷電容器。陶瓷電容器已知包括交錯內電極層和陶瓷介質。一向且未來繼續需降低成本，和縮小陶瓷電容器，不犧牲電容品質。此等需要常常兩難，因為典型上，當微電子裝置愈小、愈廉價，則裝置的品質亦降。如此導致精於此道之士，繼續努力推進電容器技術及其製造。
迄今已倡議製造陶瓷介質粉末之新技術，以提高陶瓷介質粉末之均質性，因而降低微電子裝置之尺寸和成本，同時維持此類裝置之品質。傳統上，陶瓷介質粉末之製法是，把陶瓷粉末混合物，與或不與燒結助劑以物理方式混拌。然而，典型上，在傳統混拌方法中，混拌物本質上不均勻，因為混合物之各成份有不同的粒徑分佈、顆粒形態和表面性能。結果，燒製的陶瓷在化學上為非均質性，且含有胞孔和空隙。雖然胞孔和空隙的存在，在昨日的微電子裝置可適用，但有胞孔和空隙之此等非均質性陶瓷，卻不適於今日之薄層微電子裝置。
Bergna等人的美國專利第5,082,810號提供均質塗佈陶瓷介質粉末之措施。此專利揭示把次要成份均質分佈在主要成份上之方法。此方法包含以控制流量，對乾陶瓷粉末添加多座配位子之濃縮安定溶液，同時在粉末的液體限度下激烈攪拌。再將粉末乾燥、煅燒，將金屬鉗合物分解，並除去揮發性殘餘物。多座金屬鉗合物包括溶劑內金屬化合物與界定為複座配合子的鉗合劑之混合物。鉗合劑用來提高金屬化合物在水性或水性/有機溶劑內之溶解度。此專利教示鉗合劑所提供增進溶解度，是在液體限度下充分塗佈乾粉末所必要。然而，多座鉗合物在燃燒之際，常難以藉熱力除去。
均質塗佈陶瓷介質粉末之其他策略，包含Bergna等人的美國專利第5,011,804號，揭示一種陶瓷介質組成物和方法，增進如此組成物在低燃燒溫度時之燒結率。陶瓷介質組成物的燒結率可藉改進硼酸鋅為本的燒結助熔劑均勻分佈於全體組成物，加以限制和增進。然而，使用硼酸鋅為助熔劑並非較佳，因為硼酸塩不易燒掉，導致不良的鋅殘留物，對電子裝置為致命傷。Nanao等人的美國專利第4,579,594號記載無機複合物材料之製造，係利用含至少二種金屬的溶液分解，包括金屬烷氧化物寡聚物、金屬鉗合物和醛，將金屬組成物溶解於有機溶劑內。此法不能應用於塗佈微細陶瓷粒，因為小粒結成大凝聚物之故，不適合生產平滑陶瓷。此外，許多電子應用中較佳之多相陶瓷體，尚未能製成。Pechini的美國專利第3,330,697號記載鹼土金屬和鉛的鈦酸塩、鈮酸塩和鍺酸塩之製法，係將相對應金屬鉗合物與多元醇聚合，生成摻雜物均勻分佈於陶瓷粒全體。
含有多層陶瓷電容器的微電子裝置進一步降低成本之方法，包含使用基礎金屬，諸如Ni、Cu和80 Ni：20 Cu，做為內電極材料，而非貴金屬電極，諸如Pt、Pd、Au、Ag，及其組合。Ni和Cu等基礎金屬係導電性的較低廉金屬，其純型不易氧化。二者均可使用絹印法，以沉積貴金屬的習用同樣設備，沉積做為電極。Ni的熔點較高(Ni熔點1450℃，Cu熔點1083℃，見Weast《化學物理手冊》，第46版)，對在較高溫度燃燒的多層陶瓷電容器(MLCC)有利。
鎳之一缺點是，在陶瓷介質燒結所需狀況下有氧化傾向。與氧化相關的問題因陶瓷在還原氛圍內燒結而緩和，因此確保金屬保留金屬性狀態。可惜，在還原氛圍內燒結的陶瓷，比電阻較低，非常不宜。所以，進行後燒結的再氧化步驟，使陶瓷有所需高度比電阻。
在還原氛圍內燒製，已構想過各種C0G電容器。C0G電容器有很低溫漂移的電容溫度係數(TCC)(≦±30 ppm/℃)。典型上，陶瓷主要成份包含鈦酸鎂或鈦酸鋇鉬為本之材料。迄今揭示過多種非還原型介質陶瓷組成物，包含美國專利號碼5,204,301；6,118,648；6,295,196；6,396,681；6,327,311；6,525,628；6,572,793；6,645,897和6,656,863，以及公告之專利申請案號US 2005/0111163；US 2003/0186802和US 2004/0220043號。此等內容均針對Ca、Sr、Zr、Ti、Ba氧化物的各種組合，不論有無限量的摻雜氧化物，或鹼金屬、鹼土金屬和稀土金屬，其中個別母質燒製成陶瓷矩陣。此等陶瓷雖有益，關係C0G效能仍有遜色。
傳統上，尚無必要均質塗佈的非還原性第一類介質陶瓷，因為此等多層陶瓷電容器所用介質厚度較大(5 μm或以上)。然而，今日最適介質效能之需要增加，以使用於薄層C0G裝置，但由於介質厚度減小(在~3 μm以下)，任何顆粒添加物均效率較差，與介質效能互低。然而，目前為均質塗佈陶瓷介質粉末之上述解決方式，常需用到鉗合物，以提高溶解度，並針對抗還原性C0G陶瓷介質，與上述標準陶瓷介質有相當不同的性能。
因此，技術上迄今努力提供改進性能之電容器，尤其是提供抗還原性C0G陶瓷粉末，具有高度均質化學。為此目的，本發明提供抗還原性C0G陶瓷粉末，均質塗佈摻雜物、助熔劑，和/或其他改質劑，用於下一代薄層C0G裝置，及粉末之製法。
本發明第一目的，在於製造MLOC裝置，符合C0G規格的電容溫度係數(≦±30 ppm/℃)。
本發明第二目的，在於提供具有高CV(每單位容積之電容)之基礎金屬電極多層陶瓷電容器(BME MLCC)。
本發明另一目的，在於提供一種電容器及製法，具有高度均質性化學，不用多座鉗合物。
本發明再一目的，在於提供符合C0G規格的MLCC電容器，可以能夠與較低效能裝置競爭的價格製造，諸如符合C0H、C0J、C0K、SL、R2J、X7R等，以及較低規格，以及符合工業標準，以求可靠性。
上述和其他目的可藉用下式(1)之陶瓷組成物符合：{[(CaO)t (SrO)1 － t ]w [(ZrO2 )v (TiO2 )1 － v ]}1 － s － x － y － z As Ex Gy Hz (1)其中{[(CaO)t (SrO)1 － t ]w [(ZrO2 )v (TiO2 )1 － v ]}為第一成份，而為第二成份。此外，A是過渡金屬氧化物；E是III族或IV族元素之氧化物，或其混合物；G是II族元素之氧化物；H是Y或鑭系金屬之氧化物，或其混合物；w為0.95至1.05；t為0.50至1.0；v為0.8至1.0；s為0.0001至0.08；x為0至0.08；y為0至0.20；z為0至0.20。第二成份是以溶液型式均質塗佈在該第一成份上，無多座鉗合物。
另一具體例為提供電容器之形成方法，包括：研磨包括下式之材料：[(CaO)t (SrO)1 － t ]w [(ZrO2 )v (TiO2 )1 － v ]其中W為0.95至1.05；t為0.50至1.0；v為0.8至1.0；因而形成第一成份粒(C1)；把Mn的氧化型研磨至0.50 μm以下之D50，因而形成第二成份(C2)；把SiO2 研磨至0.50 μm以下之D50，因而形成第三成份(C3)；將第二成份和第三成份及溶劑合併，因而形成第四成份(C4)，呈溶液型式，其中第四成份不含多座鉗合物；以第四成份均質塗佈第一成份粒，係在液體限度以下均勻混合第一成份，並分散第四成份，因而形成第五成份(C5)；從第五成份除去溶劑；以第二成份研磨第五成份，形成漿液；把漿液施加於膠帶，陶瓷塗佈重量為5－40 g/m2 ；從漿液除去第二溶劑，形成生塗料；把包括電極材料和填料之油墨，沉積在生塗料上，形成電容器胚材；把電容器胚材切片，形成單一多層生晶片；單一多層生晶片在PO2 為10－ 6 至10－ 1 6 的氛圍內燒製；形成接端，與電極材料呈電氣接觸。
又一具體例是提供電容器之形成方法，包括：在混合器充填芯材，包括：[(CaO)t (SrO)1 － t ]w [(ZrO2 )v (TiO2 )1 － v ]把溶液分散入混合器內，溶液包括：MnO，其D50在0.50 μm以下；SiO2 ，其D50在0.50 μm以下；以及溶劑其中溶液不含多座鉗合物；又其中溶液是在液體限度下均質塗佈於芯材，因而形成均勻塗佈之芯材；把塗佈之芯材乾燥；以第二溶劑把乾燥之塗佈芯材研磨，形成漿液；將漿液施用於膠帶，陶瓷塗佈重量為5－40 g/m2 ；從漿液除去第二溶劑，形成生塗料；把包括電極材料和填料的油墨，沉積在生塗料上，形成電容器胚材；將電容器胚材切片，形成單一多層生晶片；單一多層生晶片在PO2 為10－ 6 至10－ 1 6 的氛圍內燒製；形成接端，與電極材料呈電氣接觸。
在又一具體例內，提供一種陶瓷組成物，具有下式：{[(CaO)t (SrO)1 － t ]w [(ZrO2 )v (TiO2 )1 － v ]}1 － s － x － y － z As Ex Gy Hz 其中A為過渡金屬氧化物；E為選自Ⅲ族、Ⅳ族元素之氧化物，及其混合物；G為Ⅱ族元素之氧化物；H為選自Y、鑭系金屬元素之氧化物，及其混合物；w為0.95至1.05；t為0.50至1.0；v為0.8至1.0；s為0.004至0.04；x為0.001至0.05；y為0至0.05；而z為0至0.05。
使用基礎金屬做為電容器電極內之導電金屬，得以維持電容器內之效能，同時降低材料成本。第1圖是習知多層或堆疊陶瓷電容器1之側視圖。導電板3,5做為電極，以交替順序連接至接端7,9。電極利用介質陶瓷11加以分開和隔離。樹脂12包含電容器的一部份，一如已知技術。
電極3,5可由任何導電材料製成，但典型上為貴金屬，諸如Pt、Pd、Au或Ag。由於貴金屬難以氧化，當堆疊生板燒製時，可用高溫和氧化性氛圍，可得具有高度介質常數之陶瓷。可得電容之優良溫度係數。
使用基礎金屬，諸如Ni、Cu，及其混合，做為電極，需要修改陶瓷的組成份和燒製條件。需要低電容溫度係數(TCC)，最好符合EIA C0G標準(≦±30 ppm/℃)。
較佳陶瓷按照式(1)界定：{[(CaO)t (SrO)1 － t ]w [(ZrO2 )v (TiO2 )1 － v ]}1 － s － x － y － z As Ex Gy Hz (1)
在式(1)中，A為過渡金屬氧化物，宜選自Cu、Mn、Mo、W、Co、Ta、Sc、Hf、V、Nb、Cr，及其組合；更好是，A為氧化錳，E為III或IV族元素之氧化物，宜選自Ge、Si、Al、Ga、B，及其組合。G為II族元素之氧化物，宜選自Mg、Ca、Sr和Ba，及其組合。H為Y或鑭系金屬之氧化物，宜選自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu，及其組合。式(1)中的附屬字母具有下列數值：w為0.95至1.05，t為0.50至1.0，s為0.0001至0.08，v為0.8至1.0，x為0至0.08，y為0至0.20，z為0至0.20。最好是s為0.004至0.04，x為0.001至0.05，y為0至0.05，z為0至0.05。
式(1)化合物之獨特性為，以[(CaO)t (SrO)1 － t ]w [(ZrO2 )v (TiO2 )1 － v ]界定之母質材料，與摻雜氧化物的母質適量混合。技術上典型採用的方法包含，把諸如碳酸塩等氧化物母質之混合物加以燒製，因而形成單相主要材料和次要相，視反應物和相組成份以及燒結條件而定。氧化物母質係按上述加熱後之氧化物材料。特佳的氧化物母質包含氧化物、碳酸塩、草酸塩、過氧化物、乙酸塩、硝酸塩等。在本案中，主要相預定為CaSrZrTi氧化物材料，添加摻雜劑，形成之相，大致形成與鈣、鍶、鋯、鈦之氧化物母質和摻雜劑燒製所形成者不同。正如專於此道之士所公認，組成份之小小變化，不論是全面或局部，造成之相既非可預計，亦非可控制。所以，以先前技術，可形成偶然的次要相，逐批不同，故電容器之間亦有異。製成的材料大為改進陶瓷的一致性，就按照先前技術所形成陶瓷材料之C0G提供實際優點。
特佳配方是提供基礎材料(CaO)0 . 7 (SrO)0 . 3 (ZrO2 )0 . 9 7 (TiO2 )0 . 0 3 ，最好摻咱Mn氧化物，諸如MnO、MnO2 、MnCO3 之一或以上，以及Si氧化物，諸如SiO2 。甚至更佳的基礎材料配方(CaO)0 . 7 (SrO)0 . 3 (ZrO2 )0 . 9 7 (TiO2 )0 . 0 3 是以MnO和SiO2 組合物為摻雜材料。由於二氧化矽和二氧化錳及其母質間存在明顯的增效性，造成燒製陶瓷之改進燒結性、改進絕緣抵抗性，以及具有基礎金屬電極的薄層一級多層電容器之優異電氣效能。其他錳添加劑亦屬有益，包含硝酸錳或乙酸塩溶液，可為完全強度或稀釋水中。
又一較佳陶瓷按下式(2)界定：{[(CaO)t (SrO)1 － t ]w [(ZrO2 )v (TiO2 )1 － v ]}1 － α － β － s － x － y － z (MnO2 )α (SiO2 )β As Ex Gy Hz
除添加MnO2 和SiO2 外，式(2)和式(1)一致。式(2)註記值和式(1)相同，而α為0.0001至0.08，β為0至0.08。最好是α為0.004至0.04，β為0.001至0.05。
然而，發現為求最佳結果和電容，氧化矽和二氧化錳必須與基礎成份粒均勻混合，使氧化矽和二氧化矽均勻塗佈於基礎成份粒的全面。此特別有用於介質厚度在2 μm以下的次一代薄層C0G裝置。將添加劑以溶液塗佈於基礎成份粉粒表面，以形成高度均質性塗佈一級抗還原性介質粉末，最能達成本發明均勻混合。尤有進者，基礎成份粉粒(CaO)0 . 7 (SrO)0 . 3 (ZrO2 )0 . 9 7 (TiO2 )0 . 0 3 宜置入V型混拌器、双錐型混合器等裝置內，對粉末施以震動和研磨動作，模擬流動床。把次要成份溶解，典型上呈微細膠體懸浮液或可溶性化合物形式，諸如乙酸塩或硝酸塩溶液等。次要成份再以第11圖所示小心計量方式，添加於主要成份。在第11圖中，所示V型混拌器16具有配管強化棒17，把溶解之次要成份以小心計量方式通過液體計量和/或輸送系統19分散，把次要成份的均質混合液體和/或膠體塗料，施加於主要成份粒18。高速混合是在液體限度以下，確保粉末永遠不會太飽和液體而開始凝結。粉末在混合中，於真空20下加熱至乾。乾燥後，取出塗佈粉末，備用於混合、研磨、塗佈作業，製成介質膠帶，可用於多層陶瓷電容器。另外，粉末可進一步在400－800℃範圍內進一步加熱處理，大約30分鐘或以下，以便使乾燥之次要成份和基礎成份粒預反應，和/或除去乾燥後由塗佈溶液留下的剩餘有機殘餘物，諸如乙酸塩、硝酸塩等。如此可製成均質摻雜粉末，可耐研磨和混合操作。
上述基礎成份粒的均質塗佈又一例，包含把主要成份粉末添加於混合器，諸如V型混拌器，具有強化棒，並安裝加熱夾套。把基礎成份粉末震動，並加熱至適當溫度，從室溫至50℃。經閥計量溶解之次要成份，在混合中經強化棒添加。此項添加可藉泵或加壓裝置，或藉混拌器內維持真空，強制該次要成份通過配管的強化棒為之。液體化學可修飾，視需要包含一種成份以上，並加添加其他溶液，以方便需要時塗佈於粉末。在液體限度以下之高速混合，利用液體之毛細管作用，以均勻液體塗佈方式，塗佈基礎成份粉末。需要適當製程控制，確保粉末不會太飽和液體以致粉末開始凝結。俟次要成份添加於基礎成份粒後，塗佈粉末在真空下，放大約80℃和100℃間乾燥，直至失重穩定，或直到大約10－30分鐘的設定時間達成較大真空為止。乾燥粉末即可取出，在旋轉式煅燒器或其他清淨氛圍，於大約400－800℃反應，俾使次要成份與基本成份粒表面預反應，故對塗佈粉末賦予足夠機械完整性，以防在混合和研磨操作或其他後續處理中，從主要粉末表面除去添加劑。
俟基礎成份粒均質塗佈後，所有配方均在漿液，或諸如水、醇、甲苯等適當研磨溶液，或其組合，或二氫萜二醇(DHT)或其他適當研磨溶液內之注漿階段，使用適當媒質，研磨至D5 0 尺寸約<0.5 μm或以下。注漿使用任何適當塗佈裝置，諸如刮刀，分配在載體薄膜材料上。電極宜使用裝基礎配方或其他適用品之導電性油墨充填器，經絹印沉積。將晶片切片，在PO2 等於約10－ 8 或以下之還原性氛圍內燒出和燒製。可選用燜熱溫度1245℃至1350℃。
C0G陶瓷電容器可用MnO2 和SiO2 量介於0和8莫耳%間製成。再者，本發明不必使用多座鉗合物，形成摻雜物均質塗佈在顆粒表面，而是利用只有單座鉗合物形成均質塗佈。又，次要成份內不用硼酸鋅，亦可得均質塗佈。
積層陶瓷電容器之製備已載於文件，除上述均勻塗佈基礎成份粒之技術外，本發明不需改變製法至離技術上已知標準程序至任何重大程度。
製法之又一例是，在基礎成份顆粒已均質塗佈次要成份後，將上述陶瓷成份與分散劑，在水或有機溶劑，諸如乙醇、異丙醇、甲苯、乙酸乙酯、乙酸丙酯、乙酸丁酯、礦油精或其他適當烴液，或其混拌物內加以混拌和研磨。研磨後，添加粘結劑和塑化劑，以控制其流電性，並賦予膠帶強度，製成陶瓷注漿。所得注漿再利用膠帶鑄造法，把粘結劑和溶劑之外，陶瓷塗佈重量約5－40 g/m2 ，塗佈處理成薄片。乾燥後，除去任何溶劑，例如使用絹印法，形成印刷陶瓷片，在片上印成複數電極圖案。
積材生體是在聚碳酸酯、聚酯等物質上疊置下列製成：(1)代表底蓋之一定數量未印刷陶瓷片，然後(2)按交替方向，一定數量之印刷陶瓷片，產生交替電極，接端在相反端，以及(3)代表頂蓋之一定數量未印刷陶瓷片。印刷和未印刷片材的疊置順序變化，可用於本發明介質材料。疊堆在20℃和120℃間施壓，促進全部積層之粘著。
再把積層生體切成個別生晶片。
將生晶片加熱除去粘結劑。粘結劑可在空氣氛圍，或中性或稍具還原性氛圍內，於約200－400℃加熱約0.5至48小時而除去。
介質再於還原性氛圍內，以氧氣分壓10－ 4 至10－ 1 6 大氣壓，在不超過1350℃的溫度燒結。較佳溫度約1,200至1,325℃。燒結後，介質在氧氣分壓約10－ 5 至10－ 1 0 atm，於不超過約1,100℃的溫度加熱而再氧化。更好是在約800至1,100℃的溫度進行再氧化。此階段所得材料，典型上稱為燒結晶片。
燒結晶片按已知技術，用桶或噴砂在端面磨光，接著轉移外電極糊劑，形成外部電極。進行進一步烘焙，完全形成外電極。進一步烘焙是在氮或稍微氧化性氛圍內，於約600－1000℃溫度進行約0.1至1小時。
鎳和錫或其他適用焊劑組成物之諸層，即置於外電極上，以增進焊接性，並防止外電極的氧化。
實施例1
取基礎配方(CaO)0 . 7 (SrO)0 . 3 (ZrO2 )0 . 9 7 (TiO2 )0 . 0 3 ，放入諸如V型混拌器、双錐混合器等裝置內，對粉末賦予震動作用，模擬流動床。含MnO2 (J.T.Baker)和SiO2 (Degussa Aerosil OM50)之次要成份，各研磨至D50在0.50 μm以下，與溶劑組合。次要成份再溶化成微細膠體懸浮液型式，或可溶性化合物，諸如乙酸塩或硝酸塩溶液等。不用多座鉗合物。MnO2 和SiO2 以小心計量方式添加於基礎配方，藉用配管強化棒，直至次要成份均質塗佈在基礎配方成份上。配管強化棒維持液體計量和/或輸送系統，使次要成份之均質混合液體和/或膠體塗佈於基礎配方。高速混合是在液體限度下，以確保粉末不會太飽和液體而開始凝結。粉末再在真空下加熱至乾，同時混合除去任何溶劑。均質塗佈粉末再混合入研磨溶液內，在具有1 mm球形媒體的水平式鋼珠研磨機內，研磨到D5 0 ＝0.35 μm。膠帶經膠帶鑄造機使用刮刀塗佈，目標塗佈重量為30 g/m2 。除去任何溶劑，形成生塗料。Ni電極使用適當油墨，經絹印沉積。切片達成單一多層生晶片元件後，藉熱燒法除去單MLCC的有機材料。切片分別在1265℃、1305℃和1325℃燒製，先在約PO2 ＝10－ 6 至10－ 1 6 的耗氧氛圍內，接著是在氧氣分壓約10－ 9 atm，於1000℃之再氧化步驟。切片在角隅修圓，以適當的厚銅膜為終端。然後測量電容值。咸信以組成物為函數，在此等晶切和類似晶片之間，比較物理性能，則0.1925%和3.7787% MnO2 (同樣SiO2 量)，會產生第2－10圖所示結果。使用上述組成物和塗佈技術，可得2 μm以下之介質層。
上揭類型之電容器，可取代聚合物膜電容器，Al、Nb和Ta電容器，或現有貴金屬或基礎金屬電極為本之MLCC電容器。此類配方可得較低成本且較優異之TCC。
本發明係就特殊實施例加以說明，但非限制本發明範圍。凡精於此道之士顯而易知之修改，均認定在本發明範圍內。
1．．．多層陶瓷電容器
3,5．．．導電板
7,9．．．接端
11．．．介質陶瓷
12．．．樹脂
16．．．V型混拌器
17．．．配管強化棒
18．．．主要成份粒
19．．．液體計量/輸送系統
20．．．真空
第1圖為本發明多層陶瓷電容器側視圖；第2至4圖為摻雜劑含量對代表性陶瓷組成物電容效應之三維度圖；第5至7圖為燒製溫度對代表性陶瓷組成物電容效應之三維度圖；第8至10圖為組成份對代表性陶瓷組成物極限崩壞電壓(UVBD)效應之三維度圖；第11圖表示具有強化棒之代表性V型混拌器。
1．．．多層陶瓷電容器
3,5．．．導電板
7,9．．．接端 11．．．介質陶瓷
12．．．樹脂

Claims (42)

  1. 一種多層陶瓷電容器內之介質陶瓷組成物，包括下式之組成物：{[(CaO)t (SrO)1-t ]w [(ZrO2 )v (TiO2 )1-v ]}1-s-x-y-z As Ex Gy Hz 電容溫度係數為±30℃，其中{[(CaO)t (SrO)1-t ]w [(ZrO2 )v (TiO2 )1-v ]}做為第一成份；而As Ex Gy Hz 做為第二成份；其中A為選自包含Cu、Mn、Mo、W、Co、Ta、Sc、Hf、Nb、Cr組群的元素之氧化物，及其組合物；E為選自包含Ge、Si、Ga、B組群的元素之氧化物，及其組合物；G為Ⅱ族元素之氧化物；H為選自Y、鑭系金屬元素之氧化物，及其混合物；w為0.95至1.05；t為0.50至1.0；v為0.8至1.0；s為0.0001至0.08；x為0至0.08；y為0至0.20；z為0至0.20；又其中該第二成份係以溶液形式均質塗佈在該第一成份，無多座鉗合物者。
  2. 如申請專利範圍第1項多層陶瓷電容器內之介質陶瓷組成物，其中G為選自包含Mg、Ca、Sr和Ba組群的元素之氧化物，及其組合物；而H為選自包含Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu組群的元素之氧化物，及其組合物者。
  3. 如申請專利範圍第2項多層陶瓷電容器內之介質陶瓷組成物，其中s為0.004至0.04，x為0.001至0.05，y為0至0.05，而z為0至0.05者。
  4. 如申請專利範圍第1項多層陶瓷電容器內之介質陶瓷組成物，其中A為Mn之氧化物，而E為Si二氧化物者。
  5. 如申請專利範圍第1項多層陶瓷電容器內之介質陶瓷組成物，其中該第二成份為微細膠體懸浮液者。
  6. 如申請專利範圍第1項多層陶瓷電容器內之介質陶瓷組成物，其中該第二成份為可溶性化合物者。
  7. 如申請專利範圍第6項多層陶瓷電容器內之介質陶瓷組成物，其中該可溶性化合物係選自硝酸塩化合物、乙酸塩化合物，及其混合物者。
  8. 如申請專利範圍第1項多層陶瓷電容器內之介質陶瓷組成物，其中該第二成份係利用在液體限度下均勻混合該第一成份，並分散該第二成份，而均勻塗佈於該第一成份者。
  9. 如申請專利範圍第8項多層陶瓷電容器內之介質陶瓷組成物，其中該第二成份係在混合器內均質塗佈於該第一成份，而該混合器具有分散器，以控制該第二成份之釋除者。
  10. 如申請專利範圍第9項多層陶瓷電容器內之介質陶瓷組成物，其中該混合器係V型混拌器者。
  11. 一種多層陶瓷電容器內之介質陶瓷組成物，其中該電容器使用基礎金屬為內電極材料，以及申請專利範圍第1項之介質陶瓷組成物者。
  12. 一種電容器之形成方法，包括步驟為：把包括下式之材料加以研磨：[(CaO)t (SrO)1-t ]w [(ZrO2 )v (TiO2 )1-v ]其中w為0.95至1.05；t為0.50至1.0；而v為0.8至1.0； 因而形成第一成份粒(C1)；把Mn化合物研磨至D50低於0.50 μm，因而形成第二化合物(C2)；把SiO2 研磨至D50低於0.50 μm，因而形成第三成份(C3)；將該第二成份和該第三成份與溶劑組合，因而形成溶液形式之第四成份(C4)，其中該第四成份不含多座鉗合物；以該第四成份均勻質塗佈該第一成份粒，係在液體限度下均勻混合該第一成份，並分散該第四成份，因而形成第五成份(C5)；從該第五成份除去該溶劑；把該第五成份與第二溶劑研磨，形成漿液；把漿液施加於膠帶，陶瓷塗佈重量為5-40 g/m2 ；從該漿液除去該第二溶劑，形成生塗料；把包括電極材料和填料之油墨，沉積在該生塗料上，形成電容器胚材；把該電容器胚材切片，形成單一多層生晶片；該單一多層生晶片在PO2 為10-8 至10-16 氛圍內燒製；因而形成之電容溫度係數為±30℃之陶瓷材料；並且形成接端，與該電極材料呈電氣接觸者。
  13. 如申請專利範圍第12項之方法，又包括：在該項均質塗佈該第一成份之前，把選自包含A族、E族、G族和H族組群之至少一氧化物母質研磨，與該第二成份和該第三成份及該溶劑加以組合，其中該A族包含過渡金屬氧化物母質，該E族包含選自III族、IV族之氧化物母質，及其混合物，該G族包含II族氧化物母質，而H族包含選自Y、鑭系金屬之氧化物母質，及其混合物者。
  14. 如申請專利範圍第13項之方法，其中該A族、該E族、該G族和該H族之存在量，足以在燒製後，提供下列組 成份之陶瓷：{[(CaO)t (SrO)1-t ]w [(ZrO2 )v (TiO2 )1-v ]}1-α-β-s-x-y-z (MnO2 )α (SiO2 )β As Ex Gy Hz 其中w為0.95至1.05，t為0.50至1.0，v為0.8至1.0，α 為0.0001至0.08，β 為0至0.08，s為0.0001至0.08，，x為0至0.08，y為0至0.20，而z為0至0.20者。
  15. 如申請專利範圍第13項之方法，其中該A族、該E族、該G族和該H族存在量，足以在燒製後，提供下列組成份之陶瓷：{[(CaO)t (SrO)1-t ]w [(ZrO2 )v (TiO2 )1-v ]}1-α-β-s-x-y-z (MnO2 )α (SiO2 )β As Ex Gy Hz 其中w為0.95至1.05，t為0.50至1.0，v為0.8至1.0，α 為0.0001至0.08，β 為0至0.08，s為0.0001至0.08，，x為0至0.08，y為0至0.20，而z為0至0.20者。
  16. 一種電容器，由申請專利範圍第12項之方法形成者。
  17. 如申請專利範圍第12項之方法，其中該第四成份為微細膠體懸浮液者。
  18. 如申請專利範圍第12項之方法，其中該第四成份為可溶性化合物者。
  19. 如申請專利範圍第18項之方法，其中該可溶性化合物係選自硝酸塩化合物、乙酸塩化合物，及其混合物之形式者。
  20. 如申請專利範圍第12項之方法，其中該第四成份係在混合器內均質塗佈於該第一成份，該混合物具有分散器，以控制該第四成份之釋出者。
  21. 如申請專利範圍第20項之方法，其中該混合器為V型混拌器者。
  22. 如申請專利範圍第12項之方法，其中該第五成份係在清淨氛圍內反應，在該第五成份研磨之前，令第四成份與該第一成份粒預反應者。
  23. 一種電容器之形成方法，包括： 在混合器充填芯材，包括：[(CaO)t (SrO)1-t ]w [(ZrO2 )v (TiO2 )1-v ]把溶液分散於該混合器內，該溶液包括：MnO，其D50低於0.50 μm；SiO2 ，其D50低於0.50 μm和溶劑；其中該溶液不含多座鉗合物；又其中該溶液在液體限度下，均質塗佈該芯材，因而形成均勻塗佈之芯材；將該塗佈芯材乾燥；該乾燥之塗佈芯材以第二溶劑研磨，形成漿液；把該漿液施加於膠帶，陶瓷塗佈重量為5-40 g/m2 ；從該漿液除去該第二溶劑，以形成生塗料；把包括電極材料和填料之油墨，沉積於該生塗料上，形成電容器胚材；把該電容器胚材切片，形成單一多層生晶片；將該單一多層生晶片在PO2 為10-8 至10-16 氛圍內燒製；因而形成之電容溫度係數為±30℃之陶瓷材料；並且形成接端，與該電極材料呈電氣接觸者。
  24. 如申請專利範圍第23項電容器之形成方法，其中w為0.95至1.05，t為0.50至1.0，而v為0.8至1.0者。
  25. 一種電容器，由申請專利範圍第23項之方法形成者。
  26. 如申請專利範圍第23項之方法，其中該溶液係微細膠體懸浮液者。
  27. 如申請專利範圍第23項之方法，其中該溶液係可溶性化合物者。
  28. 如申請專利範圍第23項之方法，其中該可溶性化合物 係選自硝酸塩化合物、乙酸塩化合物，及其混合物之形式者。
  29. 如申請專利範圍第23項之方法，其中該混合物包括分散器，以控制該第四成份之釋出者。
  30. 如申請專利範圍第29項之方法，其中該混合器為V型混拌器者。
  31. 如申請專利範圍第23項之方法，其中該塗佈芯材在清淨氛圍內反應，在該乾燥之塗佈芯材研磨之前，令溶液與該芯材預反應者。
  32. 一種多層陶瓷電容器內之介質陶瓷組成物，包括下式之組成物：{[(CaO)t (SrO)1-t ]w [(ZrO2 )v (TiO2 )1-v ]}1-s-x-y-z As Ex Gy Hz ，電容溫度係數為±30℃，其中A為選自包含Cu、Mn、Mo、W、Co、Ta、Sc、Hf、Nb、Cr組群的元素之氧化物，及其組合物；E為選自包含Ge、Si、Ga、B組群的元素之氧化物，及其組合物；G為Ⅱ族元素之氧化物；H為選自Y、鑭系金屬元素之氧化物，及其混合物；w為0.95至1.05；t為0.50至1.0；v為0.8至1.0；s為0.004至0.04；x為0.001至0.05；y為0至0.05；而z為0至0.05者。
  33. 如申請專利範圍第32項多層陶瓷電容器內之介質陶瓷組成物，其中： {[(CaO)t (srO)1-t ]w [(ZrO2 )v (TiO2 )1-v ]}做為第一成份；而As Ex Gy Hz 做為第二成份；其中該第二成份係以溶液形式均質塗佈於該第一成份上，無多座鉗合物者。
  34. 如申請專利範圍第32項多層陶瓷電容器內之介質陶瓷組成物，其中G為選自包含Mg、Ca、Sr、Ba組群元素之氧化物，及其組合物；而H為選自包含Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu組群元素之氧化物，及其組合物者。
  35. 如申請專利範圍第32項多層陶瓷電容器內之介質陶瓷組成物，其中A為Mn之氧化物，E為Si之氧化物者。
  36. 如申請專利範圍第32項多層陶瓷電容器內之介質陶瓷組成物，其中該第二成份係微細膠體懸浮液者。
  37. 如申請專利範圍第32項多層陶瓷電容器內之介質陶瓷組成物，其中該第二成份係可溶性化合物者。
  38. 如申請專利範圍第37項多層陶瓷電容器內之介質陶瓷組成物，其中該可溶性化合物係選自硝酸塩化合物、乙酸塩化合物，及其混合物之形式者。
  39. 如申請專利範圍第32項多層陶瓷電容器內之介質陶瓷組成物，其中該第二成份係均質塗佈在該第一成份上，利用該第一成份在液體限度下均勻混合，並將該第二成份分散者。
  40. 如申請專利範圍第39項多層陶瓷電容器內之介質陶瓷組成物，其中該第二成份係在混合器內均質塗佈於該第一成份上，該混合器具有分散器，以控制該第二成份之釋出者。
  41. 如申請專利範圍第40項多層陶瓷電容器內之介質陶瓷組成物，其中該混合器係V型混拌器者。
  42. 一種多層陶瓷電容器內之介質陶瓷組成物，其中該電容器使用基礎金屬為內電極材料，以及申請專利範圍第32項之介質陶瓷組成物者。
TW095141984A 2005-11-14 2006-11-14 多層陶瓷電容器內之介質陶瓷組成物及其電容器之形成方法 TWI401233B (zh)

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